ES2363760T3 - PROCEDURE FOR THE PREPARATION OF ANATHYDRATES OF INSTITUTED CARBOXYLIC ACIDS. - Google Patents
PROCEDURE FOR THE PREPARATION OF ANATHYDRATES OF INSTITUTED CARBOXYLIC ACIDS. Download PDFInfo
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- ES2363760T3 ES2363760T3 ES02002119T ES02002119T ES2363760T3 ES 2363760 T3 ES2363760 T3 ES 2363760T3 ES 02002119 T ES02002119 T ES 02002119T ES 02002119 T ES02002119 T ES 02002119T ES 2363760 T3 ES2363760 T3 ES 2363760T3
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- 238000000034 method Methods 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 title description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- -1 organic compounds carboxylic acids Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims 1
- 125000005594 diketone group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WJXSXWBOZMVFPJ-NENRSDFPSA-N N-[(2R,3R,4R,5S,6R)-4,5-dihydroxy-6-methoxy-2,4-dimethyloxan-3-yl]-N-methylacetamide Chemical compound CO[C@@H]1O[C@H](C)[C@@H](N(C)C(C)=O)[C@@](C)(O)[C@@H]1O WJXSXWBOZMVFPJ-NENRSDFPSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 241000718541 Tetragastris balsamifera Species 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- MCFIMQJAFAOJPD-MTOQALJVSA-J hafnium(4+) (Z)-4-oxopent-2-en-2-olate Chemical compound [Hf+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O MCFIMQJAFAOJPD-MTOQALJVSA-J 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- RLDBHKUGRPXFBF-UHFFFAOYSA-N lanthanum;hydrate Chemical compound O.[La] RLDBHKUGRPXFBF-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
SECTOR DE LA INVENCIÓN SECTOR OF THE INVENTION
La invención describe un proceso para la preparación de anhídridos de ácidos carboxílicos insaturados, en particular la reacción de un ácido carboxílico insaturado con un anhídrido de ácido carboxílico alifático de bajo peso molecular. The invention describes a process for the preparation of unsaturated carboxylic acid anhydrides, in particular the reaction of an unsaturated carboxylic acid with a low molecular weight aliphatic carboxylic acid anhydride.
ESTADO CONOCIDO DE LA TÉCNICA KNOWN STATE OF THE TECHNIQUE
El documento DE 35 10 035 describe un procedimiento para la preparación continua de anhídridos de ácidos carboxílicos mediante la reacción de acetanhídrido con un ácido carboxílico. Este procedimiento de la anhidración renovada es generalmente conocido. El documento WO 95/32940 describe un procedimiento para la síntesis de anhídridos de ácidos carboxílicos insaturados tales como, por ejemplo, anhídrido del ácido acrílico o anhídrido del ácido metacrílico, mediante una reacción de un cloruro de ácido aromático tal como, por ejemplo, cloruro de benzoílo, con los aniones del ácido carboxílico insaturado. Desde el punto de vista industrial, este procedimiento tiene el inconveniente de que por cada mol de anhídrido formado resulta un mol de cloruro de sodio en calidad de material de desecho a eliminar. DE 35 10 035 describes a process for the continuous preparation of carboxylic acid anhydrides by the reaction of acetanhydride with a carboxylic acid. This renewed anhydration procedure is generally known. WO 95/32940 describes a process for the synthesis of unsaturated carboxylic acid anhydrides such as, for example, acrylic acid anhydride or methacrylic acid anhydride, by a reaction of an aromatic acid chloride such as, for example, chloride of benzoyl, with the anions of the unsaturated carboxylic acid. From an industrial point of view, this process has the disadvantage that for each mole of anhydride formed, one mole of sodium chloride results as waste material to be removed.
El documento FR 2592040 describe la síntesis de anhídrido del ácido metacrílico mediante la reacción de anhídrido del ácido acético con ácido metacrílico en ausencia de un catalizador. Es necesario estabilizar la mezcla de reacción mediante la presencia de un inhibidor de la polimerización. FR 2592040 describes the synthesis of methacrylic acid anhydride by the reaction of acetic acid anhydride with methacrylic acid in the absence of a catalyst. It is necessary to stabilize the reaction mixture by the presence of a polymerization inhibitor.
Existe una pluralidad de posibilidades de preparar anhídrido del ácido metacrílico (MASA – siglas en alemán). Así, MASA se obtiene a partir del ácido metacrílico y del correspondiente cloruro de ácido según los documentos WO 9532940, US 4.874.558 o SU 228016. Otra vía de síntesis es la descrita como catálisis de transferencia de fases con los productos arriba mencionados en Lab. Chim. Org. CNRS, Rennes-Beaulieu, Fr. Tetrahedron (1988), 44(9), 2471-6. El documento DE 35 44 765 describe la carbonilación de ésteres del ácido metacrílico bajo catálisis con metales a elevada temperatura y elevada presión. A través de la deshidrogenación del ácido metacrílico se puede preparar asimismo MASA con los catalizadores AcOC(CN)2Me (documento JP 49034655) o (CN)2 más Ni(OAc)2. Una síntesis sencilla es la reacción de MAS y anhídrido del ácido acético (EA – siglas en alemán). En el documento DE 35 10 035, dicha reacción se describe como un proceso continuo bajo catálisis con ácido. El documento FR 2592040, en calidad de ensayo en tandas, no puede pasarse sin catalizador. There are a plurality of possibilities to prepare methacrylic acid anhydride (MASA). Thus, MASA is obtained from methacrylic acid and the corresponding acid chloride according to WO 9532940, US 4,874,558 or SU 228016. Another route of synthesis is that described as phase transfer catalysis with the products mentioned above in Lab Chim. Org. CNRS, Rennes-Beaulieu, Fr. Tetrahedron (1988), 44 (9), 2471-6. DE 35 44 765 describes the carbonylation of methacrylic acid esters under catalysis with metals at high temperature and high pressure. Through the dehydrogenation of methacrylic acid, MASA can also be prepared with the AcOC (CN) 2Me (JP 49034655) or (CN) 2 plus Ni (OAc) 2 catalysts. A simple synthesis is the reaction of MAS and acetic acid anhydride (EA). In DE 35 10 035, said reaction is described as a continuous process under acid catalysis. Document FR 2592040, as a batch test, cannot be passed without a catalyst.
El documento DE 36 44 222 describe la síntesis de anhídridos del ácido carboxílico (entre otros, en el texto se menciona de paso también ASA) en presencia de iones de metales de los grupos Mn, Fe, Co, Ni y Mg, los cuales, entre otros, se presentan también en forma de acetato. Estos metales redox tienden fuertemente a sufrir variaciones en la etapa de oxidación, lo cual se traduce desventajosamente sobre el transcurso de la reacción en el caso de la síntesis de ácidos carboxílicos insaturados y conduce a una polimerización. Por ello, en esta invención se recurre a otras sales de metales que no fomentan la polimerización. Por ello, el procedimiento contrasta con el documento DE 36 44 222, dado que se utilizan otros acetatos de metales. Además, se trabaja con depresión, lo cual está ligado a una menor solicitación de la temperatura y se utiliza el procedimiento de tandas de alimentación, con lo que aumenta el rendimiento espacio-tiempo. A partir del documento DE 36 44 222 se conoce un procedimiento en el que se preparan anhídridos de ácidos carboxílicos, en presencia de un ion metálico seleccionado del grupo Mn, Fe, Co, Ni o Mg. La reacción se lleva a cabo en un intervalo de temperaturas entre 10ºC hasta el punto de ebullición del anhídrido de ácido alifático inferior. No obstante, en este caso se hacen reaccionar preferiblemente ácidos carboxílicos aromáticos y ácidos policarboxílicos aromáticos y anhídridos de ácidos carboxílicos alifáticos inferiores. Document DE 36 44 222 describes the synthesis of carboxylic acid anhydrides (among others, ASA is also mentioned in the text) in the presence of metal ions of the groups Mn, Fe, Co, Ni and Mg, which, among others, they also come in the form of acetate. These redox metals tend to suffer variations in the oxidation stage, which translates disadvantageously over the course of the reaction in the case of the synthesis of unsaturated carboxylic acids and leads to polymerization. Therefore, in this invention other metal salts are used that do not promote polymerization. Therefore, the procedure contrasts with DE 36 44 222, since other metal acetates are used. In addition, it works with depression, which is linked to a lower temperature request and the feeding batch procedure is used, thereby increasing space-time performance. From DE 36 44 222 a process is known in which carboxylic acid anhydrides are prepared, in the presence of a metal ion selected from the group Mn, Fe, Co, Ni or Mg. The reaction is carried out in a temperature range between 10 ° C to the boiling point of the lower aliphatic acid anhydride. However, in this case, aromatic carboxylic acids and aromatic polycarboxylic acids and anhydrides of lower aliphatic carboxylic acids are preferably reacted.
MISIÓN MISSION
Existía, por lo tanto, la misión de mejorar los procedimientos conocidos para la preparación de anhídrido del ácido metacrílico en la medida en que, por una parte, se evite la precipitación de halógeno y que, en segundo lugar, mediante el uso de un correspondiente catalizador, se aumente el tiempo de reacción y el rendimiento de espacio-tiempo de la reacción de anhidración renovada. There was, therefore, the mission of improving known procedures for the preparation of methacrylic acid anhydride to the extent that, on the one hand, halogen precipitation is avoided and, secondly, by the use of a corresponding catalyst, the reaction time and the space-time yield of the renewed anhydration reaction are increased.
SOLUCIÓN SOLUTION
El problema se resuelve mediante la reacción del ácido metacrílico con anhídrido del ácido acético en presencia de un catalizador y de un inhibidor. En calidad de catalizador sirve una sal metálica de un compuesto orgánico. En calidad de metal entran en consideración los metales Cr, Zn, Ca, Na, Ti, Zr, Hf, La. El compuesto orgánico posee al menos un grupo carboxilo. The problem is solved by the reaction of methacrylic acid with acetic acid anhydride in the presence of a catalyst and an inhibitor. As a catalyst, a metal salt of an organic compound is used. As metals, metals Cr, Zn, Ca, Na, Ti, Zr, Hf, La come into consideration. The organic compound has at least one carboxyl group.
Por los compuestos orgánicos que poseen al menos un grupo carboxilo se entienden sales de ácido carboxílico de ácidos carboxílicos alifáticos inferiores tales como, por ejemplo, acetatos, propionatos, butiratos, lauratos, salicilatos, etc. y β-dicetonas tales como, por ejemplo, acetilacetonatos (2,4-pentanodionatos), 3,5-heptanodionatos y Organic compounds having at least one carboxyl group are carboxylic acid salts of lower aliphatic carboxylic acids such as, for example, acetates, propionates, butyrates, laurates, salicylates, etc. and β-diketones such as, for example, acetylacetonates (2,4-pentanedionates), 3,5-heptanedionates and
2 2
acetonatos de benzoílo o ácidos β-cetocarboxílicos tales como, por ejemplo, acetoacetatos o sales de ácidos βcetocarboxílicos tales como, por ejemplo, acetoacetatos de etilo o ácidos dicarboxílicos tales como, por ejemplo, ácido oxálico y ácido malónico. Particularmente preferidas son sales de metales en forma de los acetatos y acetilacetonatos. El catalizador puede emplearse tanto para llevar a cabo la reacción en el reactor discontinuo como 5 también en reacciones que se llevan a cabo según el procedimiento de tandas de alimentación o procedimientos continuos. Si la reacción se lleva a cabo como procedimiento de tandas de alimentación, se disponen en el reactor ácido metacrílico y la mitad del anhídrido de ácido acético y la otra mitad del anhídrido del ácido acético se aporta dosificadamente en el transcurso de la reacción. La relación molar de anhídrido del ácido acético a ácido metacrílico varía de de 0,5 a 1, preferiblemente la relación es 0,55 a 0,65, de manera particularmente preferida, la relación es de benzoyl acetonates or β-ketocarboxylic acids such as, for example, acetoacetates or salts of βcetocarboxylic acids such as, for example, ethyl acetoacetates or dicarboxylic acids such as, for example, oxalic acid and malonic acid. Particularly preferred are metal salts in the form of acetates and acetylacetonates. The catalyst can be used both to carry out the reaction in the discontinuous reactor and also in reactions that are carried out according to the process of feeding batches or continuous procedures. If the reaction is carried out as a feed batch process, methacrylic acid and half of the acetic acid anhydride are disposed in the reactor and the other half of the acetic acid anhydride is dosed in the course of the reaction. The molar ratio of acetic acid anhydride to methacrylic acid ranges from 0.5 to 1, preferably the ratio is 0.55 to 0.65, particularly preferably, the ratio is
10 0,58 a 0,62. El uso del catalizador acorta fuertemente el tiempo de reacción. Dado que el catalizador permanece en forma de un sólido o disuelto en la disolución de reacción, puede separarse también fácilmente. El anhídrido de ácido metacrílico puede separarse fácilmente mediante destilación, y la disolución de reacción, intensamente teñida en parte, no tiene efecto alguno sobre el color del producto obtenido. 10 0.58 to 0.62. The use of the catalyst strongly shortens the reaction time. Since the catalyst remains in the form of a solid or dissolved in the reaction solution, it can also be easily separated. The methacrylic acid anhydride can be easily separated by distillation, and the partially stained reaction solution has no effect on the color of the product obtained.
15 En calidad de estabilizadores pueden utilizarse todos los inhibidores habituales, entre otros hidroquinona, hidroquinona-monometiléter, Topanol O, Topanol A, fenotiazina, Irganox 1010 (marca registrada de Ciba AG) y N,N’difenil-p-fenilendiamina, así como sus mezclas. As stabilizers all usual inhibitors can be used, among others hydroquinone, hydroquinone-monomethyl ether, Topanol O, Topanol A, phenothiazine, Irganox 1010 (registered trademark of Ciba AG) and N, N'diphenyl-p-phenylenediamine, as well as their mixtures
Prescripción general del ensayo General prescription of the trial
20 Ácido metacrílico, anhídrido del ácido acético y los estabilizadores así como el catalizador se disponen en el matraz de reacción. En el equipo se hace un vacío de 95 mbar, y la tanda se calienta hasta la temperatura de ebullición. A continuación, se retira el destilado con contenido en ácido acético y se añade gota a gota de forma continua la segunda porción de anhídrido del ácido acético. 20 Methacrylic acid, acetic acid anhydride and stabilizers as well as the catalyst are arranged in the reaction flask. A vacuum of 95 mbar is made in the equipment, and the batch is heated to the boiling temperature. Then, the distillate containing acetic acid is removed and the second portion of acetic acid anhydride is added dropwise continuously.
25 Si la temperatura de cabeza se mantiene constante, se reduce lentamente la presión. Como valor final se alcanza una presión de aprox. 2-20 mbar. Después de finalizada la reacción, la tanda se enfría hasta la temperatura ambiente y el fondo de la columna se analiza mediante CG. El producto bruto tiene un contenido en MASA de 9798%. Mediante destilación fraccionada puede alcanzarse una pureza de más del 99%. 25 If the head temperature remains constant, the pressure is slowly reduced. As a final value, a pressure of approx. 2-20 mbar After the end of the reaction, the batch is cooled to room temperature and the bottom of the column is analyzed by GC. The crude product has a MASS content of 9798%. By fractional distillation a purity of more than 99% can be achieved.
30 Tanda: 30 Batch:
322,8 g (3,75 mol) de ácido metacrílico 114,9 g (1,13 mol) de anhídrido del ácido acético, dispuesto 35 114,9 g (1,13 mol) de anhídrido del ácido acético, añadido gota a gota 1,61 g (0,5% ref. a MAS) de catalizador, véase la Tabla 1000 mg (3100 ppm ref. a MAS) de fenotiazina 200 mg (620 ppm ref. a MAS) de hidroquinona 322.8 g (3.75 mol) of methacrylic acid 114.9 g (1.13 mol) of acetic acid anhydride, disposed of 114 114.9 g (1.13 mol) of acetic acid anhydride, added dropwise to drop 1.61 g (0.5% ref. to MAS) of catalyst, see Table 1000 mg (3100 ppm ref. to MAS) of phenothiazine 200 mg (620 ppm ref. to MAS) of hydroquinone
40 Ensayo Comparativo 40 Comparative Test
El Ensayo Comparativo se lleva a cabo análogamente, pero sin adición de catalizador, y se designa en la Tabla como tanda estándar. En este caso, la reacción dura más que con catalizador. Además, son menores la pureza del producto bruto y el rendimiento The Comparative Test is carried out analogously, but without catalyst addition, and is designated in the Table as standard batch. In this case, the reaction lasts longer than with catalyst. In addition, the purity of the crude product and the yield are lower
45 Tabla Resultados de los ensayos 45 Table Test results
- EjemploExample
- Composición Fondo de la columna Observaciones / catalizador Composition Column Background Remarks / catalyst
- Tiempo de reacción h Reaction time h
- MASA % en vol. Rendimiento % MASS% in vol. Performance %
- Ensayo Test
- 5,5 96,66 61,9 Tanda estándar, sin catalizador 5.5 96.66 61.9 Standard batch, without catalyst
- comparativo comparative
- acetato de cromo chrome acetate
- 1 one
- 4,25 98,35 78,2 acetato de zinc 4.25 98.35 78.2 zinc acetate
- 2 2
- 3,5 97,1 69,2 acetato de cobre, monohidrato 3.5 97.1 69.2 copper acetate monohydrate
- Ensayo Test
- 3,5 97,51 70,8 3.5 97.51 70.8
- comparativo comparative
- 4 4
- 3,5 97,14 73,9 acetato de calcio, monohidrato 3.5 97.14 73.9 calcium acetate monohydrate
- 5 5
- 4,5 96,65 72,2 acetato de sodio 4,5 96.65 72.2 sodium acetate
- 6 6
- 4,25 98,24 76,8 acetilacetonato de zirconio 4.25 98.24 76.8 zirconium acetylacetonate
- 7 7
- 4,5 96,41 65 acetilacetonato de cromo 4,5 96.41 65 chrome acetylacetonate
- 8 8
- 4 97,4 74,5 acetilacetonato de lantano-hidrato 4 97.4 74.5 Lanthanum Hydrate Acetylacetonate
- 9 9
- 4 98,56 73,5 acetilacetonato de hafnio 4 98.56 73.5 hafnium acetylacetonate
- 10 10
- 4,25 98,6 74,9 acetilacetonato de titanio 4.25 98.6 74.9 titanium acetylacetonate
3 3
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10106352A DE10106352A1 (en) | 2001-02-09 | 2001-02-09 | Process for the preparation of anhydrides of unsaturated carboxylic acids |
| DE10106352 | 2001-02-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2363760T3 true ES2363760T3 (en) | 2011-08-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES02002119T Expired - Lifetime ES2363760T3 (en) | 2001-02-09 | 2002-01-29 | PROCEDURE FOR THE PREPARATION OF ANATHYDRATES OF INSTITUTED CARBOXYLIC ACIDS. |
Country Status (6)
| Country | Link |
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| US (1) | US6936734B2 (en) |
| EP (1) | EP1231201B1 (en) |
| JP (1) | JP2002275124A (en) |
| AT (1) | ATE506339T1 (en) |
| DE (2) | DE10106352A1 (en) |
| ES (1) | ES2363760T3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2826961B1 (en) * | 2001-07-06 | 2005-09-30 | Atofina | PROCESS FOR THE PREPARATION OF (METH) ACRYLIC ANHYDRIDE |
| DE10249928A1 (en) | 2002-10-26 | 2004-05-06 | Basf Ag | Flexible process for the joint production of (i) formic acid, (ii) a carboxylic acid with at least two carbon atoms and / or its derivatives and (iii) a carboxylic acid anhydride |
| JP2005060300A (en) * | 2003-08-12 | 2005-03-10 | Mitsubishi Rayon Co Ltd | Method for producing carboxylic anhydride |
| DE10355830A1 (en) * | 2003-11-26 | 2005-06-09 | Röhm GmbH & Co. KG | Production of (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate for use e.g. in adhesives or paint, comprises transesterification of methyl methacrylate with glycerol carbonate using a metal 1,3-diketonate catalyst |
| FR2877003B1 (en) * | 2004-10-26 | 2007-01-05 | Arkema Sa | IMPROVED PROCESS FOR THE MANUFACTURE OF (METH) ACRYLIC ANHYDRIDE |
| DE102006060162A1 (en) * | 2006-12-18 | 2008-06-19 | Evonik Röhm Gmbh | Improved process for the preparation of unsaturated carboxylic acid hybrids |
| JP5032362B2 (en) * | 2007-03-12 | 2012-09-26 | ローム アンド ハース カンパニー | Hydroxyphenyl acrylate monomers and polymers |
| FR2927329B1 (en) * | 2008-02-08 | 2010-04-16 | Arkema France | IMPROVED PROCESS FOR THE PREPARATION OF (METH) ACRYLIC ANHYDRIDE |
| EP2308820B1 (en) | 2008-08-05 | 2016-12-28 | Mitsubishi Rayon Co., Ltd. | Method for producing (meth)acrylic acid anhydride, method for storing (meth)acrylic acid anhydride, and method for producing (meth)acrylate ester |
| WO2010090258A1 (en) | 2009-02-05 | 2010-08-12 | 三菱レイヨン株式会社 | Method for producing (meth)acrylate ester |
| FR2993558B1 (en) * | 2012-07-18 | 2014-08-29 | Rhodia Operations | SYNTHESIS OF (METH) ACRYLIC ANHYDRIDE BY TRANSANHYDRIFICATION |
| US9969670B2 (en) | 2014-01-20 | 2018-05-15 | Rhodia Operations | Synthesis of (meth) acrylic anhydride by transanhydrization |
| CN108129293A (en) * | 2018-01-25 | 2018-06-08 | 杭州和利时自动化有限公司 | A kind of method of synthesizing methyl acrylic anhydride |
| EP3524589A1 (en) | 2018-02-09 | 2019-08-14 | 3M Innovative Properties Company | Process for the manufacturing of a (meth)acrylic anhydride in a flow reactor |
| EP3990425B1 (en) | 2019-06-25 | 2025-01-22 | Evonik Operations GmbH | Process for distillative purification of unsaturated carboxylic anhydrides |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2319070A (en) * | 1938-03-31 | 1943-05-11 | Eastman Kodak Co | Manufacture of unsaturated aliphatic acids and anhydrides |
| FR863141A (en) * | 1939-01-30 | 1941-03-24 | Cie Des Meules Norton | Methacrylic anhydride and its manufacturing process |
| GB612790A (en) * | 1946-06-04 | 1948-11-17 | Hunter William | Improvements in the manufacture of crotonic anhydride |
| DE3544765C2 (en) | 1985-12-18 | 1994-04-07 | Roehm Gmbh | Process for the production of unsaturated aliphatic carboxylic anhydrides |
| FR2592040B1 (en) * | 1985-12-24 | 1988-07-15 | Charbonnages Ste Chimique | PROCESS FOR THE SYNTHESIS OF (METH) ACRYLIC ANHYDRIDES |
| DE3644222C2 (en) * | 1985-12-25 | 1998-03-19 | Daicel Chem | Process for the preparation of carboxylic anhydrides |
| US4874558A (en) * | 1987-05-21 | 1989-10-17 | Indiana University Foundation | Polymer catalyzed synthesis of acid anhydrides |
| WO1995032940A1 (en) | 1994-05-27 | 1995-12-07 | Howard University | Process for the production of olefin acid anhydrides and esters thereof |
-
2001
- 2001-02-09 DE DE10106352A patent/DE10106352A1/en not_active Ceased
-
2002
- 2002-01-29 EP EP02002119A patent/EP1231201B1/en not_active Expired - Lifetime
- 2002-01-29 ES ES02002119T patent/ES2363760T3/en not_active Expired - Lifetime
- 2002-01-29 AT AT02002119T patent/ATE506339T1/en active
- 2002-01-29 DE DE50215007T patent/DE50215007D1/en not_active Expired - Lifetime
- 2002-02-06 JP JP2002029706A patent/JP2002275124A/en active Pending
- 2002-02-11 US US10/068,849 patent/US6936734B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE10106352A1 (en) | 2002-08-22 |
| EP1231201A1 (en) | 2002-08-14 |
| DE50215007D1 (en) | 2011-06-01 |
| JP2002275124A (en) | 2002-09-25 |
| ATE506339T1 (en) | 2011-05-15 |
| EP1231201B1 (en) | 2011-04-20 |
| US20020161260A1 (en) | 2002-10-31 |
| US6936734B2 (en) | 2005-08-30 |
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